JPS63113538A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color reproducibility by incorporating one kind of specific coupler to a green and a red sensitive emulsion layers respectively, and by specifying the wavelength corresponding to the wavelength which displays the max. sensitivity in a spectral sensitivity of the red sensitive emulsion layer and the wavelength corresponding to 30% sensitivity of the max. sensitivity. CONSTITUTION:The green sensitive emulsion layer contains one kind of the coupler shown by formula I, and the red sensitive emulsion layer contains one kind of the coupler shown by formula II. The wavelength of the max. sensitivity in the spectral sensitivity of the red sensitive emulsion layer is a range of 600-650nm. The wavelength corresponding to 30% max. sensitivity in the spectral sensitivity is a range of 550-680nm. In the formula, Za and Zb are each =N- bond, R1 and R2 are each hydrogen atom or a substitutent, X is hydrogen atom or a group capable of releasing by coupling reaction with an oxidant of an aromatic primary amine developing agent, R3 is an aliphatic hydrocarbon group or an aryl group, etc., R4 is hydrogen atom, etc., R5 is an aliphatic hydrocarbon group, etc., R6 and R7 are each hydrogen atom or a lower alkyl group. Thus, the color reproducibility of the titled material and the preservability of the dye image are improved.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically to a silver halide color photographic light-sensitive material, which improves color reproducibility and prevents the vividness of colors from being deteriorated over time of images. This invention relates to a color photographic material containing less silver halide.

(Background technology) Silver halide color photosensitive materials (hereinafter referred to as photosensitive materials) are
A photosensitive layer consisting of three types of silver halide emulsion layers selectively sensitized to be sensitive to blue light, green light, and red light is coated on a support in a multilayer structure. For example, color films are generally coated with blue-sensitive, green-sensitive, and red-sensitive emulsion layers in order from the exposed side for both negative and reversal use, and a yellow filter layer or antihalation layer that can be whitened. , an intermediate layer, a protective layer, etc. are added as required. This layer structure is designed to be optimal depending on the purpose, such as one-color paper or color reversal paper, for example.

In order to form a color photographic image, the additive color method and the subtractive color method can be broadly classified, and the latter method usually produces yellow,
A photographic coupler that develops three colors, magenta and cyan, is contained in the photosensitive layer, and the image-exposed photosensitive material is subjected to color development processing using a color developing agent.

During color development, the aromatic primary amine of the color developing agent and the photographic coupler undergo an oxidative coupling reaction, resulting in the formation of an indophenol or azomethine coloring dye. In order to obtain a color photographic image with good color reproducibility, it is essential that the coloring dye be a bright cyan, magenta, or yellow dye with little side absorption.

Conventionally, unnecessary absorption of magenta and yellow components of cyan dyes and unnecessary absorption of yellow and cyan components of magenta dyes lead to deterioration of color reproducibility of highly saturated subjects, so in order to improve color reproducibility, Efforts have continued to reduce unwanted absorption of these dyes.

For example, as a means of improving the spectral absorption of the coloring dye of the coupler and obtaining sharp spectral absorption with little side absorption, pivaloyl type yellow couplers (U.S. Patent No. 3.
/9'1 etc.), anilino-type magenta coupler (
Pyrazolotriazole type magenta couplers (described in U.S. Patent No. 3.72!, U.S. Pat. No. 062, etc.)
etc. have been developed.

In addition, the so-called multilayer effect (described in Belgian Patent No. 710.31141, German Patent No. 2,0413, Ri-4tj, etc.), which increases color purity through the development effect, is used, and by applying this concept, so-called DIR couplers ( U.S. Patent No. 3. Co., 27, J44, etc.)
was developed. Furthermore, a method for correcting the effect of unnecessary absorption of coloring dyes using colored couplers with an automatic masking function (U.S. Patent No. 3).

4t6! , /70, etc.) have been proposed.

However, with any of these methods, fully satisfactory results regarding color reproduction have not been obtained.

JP-A-6/-223'1.2 describes that the combination of a pyrazoloazole type magenta coupler and a diacylamino type cyan coupler improves side absorption and provides better color reproduction. , and the red mentioned below
There were some imperfections in the reproduction of purple colors.

Tokukai Showa θ-, 232!60! ,! A technique is described in which color development, color reproducibility, image storage stability, and the balance thereof are improved by the combined use of an N-heterocyclic magenta coupler, an acylamino cyan coupler, and a yellow coupler. However, this technique does not solve the problem of purple and red color reproducibility mentioned above.

Also, JP-A-67-/6;7ri! It is stated that the combination of a birazolotriazole magenta coupler and a carbostyryl coupler improves the color reproducibility of hues, especially blue, and that the balance of light fastness is improved. Even with this technology, the above-mentioned problem of reproducibility of purple and red colors was not solved.

It is also known that color reproducibility is greatly affected by spectral sensitivity. In color photographic materials using the subtractive color method, it is particularly difficult to faithfully reproduce purple without deteriorating the saturation of red (great efforts have been made in the past). In order not to deteriorate the saturation of red, if the wavelength of the highest spectral sensitivity of the red-sensitive emulsion layer is relatively long, such as tto, ttonm, the color reproducibility of purple will be reproduced as a reddish-purple color lacking cyan. .

Conversely, if the spectral sensitivity of the red-sensitive emulsion layer is made slightly shorter than the above, the color reproduction of purple will be more faithful, but the sensitivity of the red-sensitive emulsion layer to red light will be insufficient, resulting in poor red color reproduction. However, it does not have a cyan tinge, which has the disadvantage of reducing saturation.

Furthermore, it is known that the color reproducibility of purple color changes and deteriorates as the image ages. For example, print sensitive material (color one/e-, color inversion one) etc.) VC
However, when a print was saved in an album, for example, the cyan component in the purple color deteriorated significantly, causing the red color to become a dull purple color.

U.S. Patent No. 31.721"2 discloses a technology known for improving the color reproducibility of color photographic materials, which reduces changes in color reproducibility when photographing under various light sources with different color temperatures. A method is disclosed.

With the spectral sensitivity specified in this patent, the spectral sensitivity of the red-sensitive emulsion layer is too short for short wavelengths, and the sensitivity of the red-sensitive emulsion layer to red light is insufficient, resulting in red color reproduction that is extremely cyan-tinged. In addition to being accompanied by a decrease in saturation, the color reproduction of purple also tends to become cyan-tinged.

For these reasons, it has been desired to improve the color reproducibility of color photographic materials, and in particular to improve the color reproducibility of violet colors without causing a decrease in red color reproducibility.

At the same time, it was desired that this color reproduction would not change even during image storage.

(Problems to be Solved by the Invention) A first object of the present invention is to provide a silver halide color photographic material with improved color reproduction. The second object of the present invention is to maintain the fidelity of color reproduction even during image storage, to maintain excellent color reproduction fidelity over a long period of time, and to improve the saturation of reproduced colors. It is an object of the present invention to provide a silver halide color photographic light-sensitive material that maintains the quality of silver halide.

(Means for Solving the Problems) The above aspects of the present invention are a silver halide color photographic light-sensitive material having at least seven red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers on a support. And,
At least one type of coupler represented by the following general formula [I] is contained in at least the green-sensitive emulsion layer, and at least one type of coupler represented by the following general formula [II] is contained in at least the red-sensitive emulsion layer. The wavelength at which the red-sensitive emulsion layer exhibits the highest spectral sensitivity is between θ0 nm and 6! θ
nm range, and the wavelength of sensitivity corresponding to the highest spectral sensitivity 3θ range is from t r o nm to 6! It has been found that this can be achieved by using a silver halide photographic light-sensitive material which is characterized in that it is in the onm range.

General formula (I) Ma = evil (in the formula, Za and Zb represent =C-4 or -N-,
R1 and R2 represent a hydrogen atom or a substituent, and X represents a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Za=Zb
When is a carbon-carbon double bond, it may be a part of an aromatic ring, and R1, Rz4 or X may form a dimer or higher multimer.

General formula [II] In formula 1, R represents an aliphatic group, an aryl group, or a heterocyclic group which may have a substituent, and R4 represents a hydrogen atom, a halogen atom, an alkyl group, or an acylamino group. R5 represents an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxy group, an aliphatic thio group, an aryloxy group, an arylthio group, or an acylamino group, R and R may be the same or different from each other, and a hydrogen atom or a lower alkyl group. X2 represents a group that can be separated during the coupling reaction with the oxidized form of the developing agent. ) As used herein, the term "aliphatic group" may be linear, branched, or cyclic, and includes saturated and unsaturated groups such as alkyl, alkenyl, and alkynyl groups.

As a magenta coupler! - When using a pyrazolone coupler, in order to improve the color reproducibility of a purple subject, if the spectral sensitivity of the red-sensitive emulsion layer is shortened as in the present invention, the sensitivity of the red-sensitive emulsion layer to red light will be reduced. lacking,
Red color reproduction becomes cyan-tinged and saturation decreases.

When a coupler represented by the general formula [■] of the present invention is used as a magenta coupler, the coloring pigment is! -Since there is less cyan component on the longer wavelength side than the color forming dye of the pyrazolone coupler, even if the spectral sensitivity of the red-sensitive emulsion layer is shortened to a short wavelength as in the present invention, in order to improve the purple color reproducibility, the magenta dye is mainly The color reproducibility of the red color reproduced with the yellow pigment has little cyan component and the saturation does not decrease.

Furthermore, as a result of extensive research, the inventors have found that when a coupler represented by the general formula [II] of the present invention is used as a cyan coupler, the storage stability of purple color images is dramatically improved, and the image can be preserved over a long period of time. It has been found that the layers also maintain excellent color reproduction.

This is because by employing the magenta coupler of the present invention and the spectral sensitivity of the short wavelength red-sensitive layer, the purple color image produced is due to the small amount of cyan components on the long wavelength side of magenta.
Because the contribution of cyan dye is large, the (heat) of cyan dye
This seems to be related to susceptibility to preservation, but the mechanism behind this is not clear.

Therefore, as in the present invention, a coupler represented by general formula (1) is used as a magenta coupler, a coupler represented by general formula (If) is used as a cyan coupler, and a red-sensitive emulsion layer according to the present invention is used. For the first time, by using shorter wavelengths, it was possible to improve the color reproducibility of purple without reducing the saturation of red, and to obtain a photosensitive material whose color image was less susceptible to the effects of aging.

Among the pyrazoloazole magenta couplers represented by the general formula (1), preferred ones are those represented by the following general formula (Ia).
, <Ib), (IC), (Id) and (Ie).

(Ia) (Ib) (Ic)
(Id) (Ie) Among the couplers represented by general formulas (Ia) to (Ie), those preferred for the purpose of the present invention are general formulas (% formula %) In general formulas (Ia) to (re), R11, R12
and R13 may be the same or different and each represents a hydrogen atom, a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic group, an acyloxy group, and a carbamoyloxy group. group, silyloxy group, sulfonyloxy group,
Acylamino group, anilino group, ureido group, imide group,
Sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group ,
It represents an alkoxycarbonyl group and an aryloxycarbonyl group, and particularly preferred are an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an acylamino group, and an anilino group. X is a hydrogen atom, a hydrogen atom, a carboxy group,
Alternatively, it represents a group that is bonded to carbon at the coupling position via an oxygen atom, nitrogen atom, or sulfur atom, and is decoupled. R, R, R13, J or X may be a divalent group to form a bis body.

It may also be in the form of a polymer coupler in which the coupler residues represented by general formulas (Ia) to (Ie) are present in the main chain or side chain of the polymer; Preference is given to polymers in which R, R, R13, J or X represent a vinyl group or a linking group.

When the vinyl monomer contains those represented by general formulas (Ia), (Ib), (IC), (Id) and (Ie), the connecting group represented by R, R, R or , alkylene group (substituted or unsubstituted alkylene group, such as methylene group, ethylene group, /, /θ-decylene group,
-CH2CH20CH2CH2-1, etc.), phenylene group (substituted or unsubstituted phenylene group, for example /, <
t-phenylene group, /I3-phenylene group, -CONH
It includes a group formed by a combination of -1-0-1-OCO- and aralkylene.

Preferred linking groups include the following.

-NHCO-1-CH2CH2-1 -CH2CH2-0-C-1 -CONH-CH2CH2NHCO-1-CH2CH2
0-CH2CH2-NHCO-1 The vinyl group may have substituents other than those represented by general formulas (Ia) to Ne), and preferred substituents are hydrogen atoms, chlorine atoms, or lower carbon atoms having 7 to 9 carbon atoms. Alkyl groups (e.g. methyl group,
ethyl group).

Monomers including those represented by general formulas (Ia) to (Ie) can be copolymerized with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers. Good too.

As is well known in the polymeric color coupler art, the non-chromogenic ethylenically unsaturated monomers to be copolymerized with the solid water-insoluble monomeric coupler depend on the physical and/or chemical properties of the copolymer formed, e.g. solubility, compatibility of the photographic colloidal composition with binders such as gelatin, its flexibility,
It can be selected so that thermal stability etc. are favorably influenced.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, but polymer coupler latex is particularly preferred.

Among the pyrazoloazole magenta couplers represented by the general formula (I), more preferable ones are the following general formula (If
), (Ig).

(If) (Ig) General formula (If)
, (Ig), R31 represents an alkyl group, and R32 represents an alkyl group, an alkoxy group, or an alkylthio group.

Among R1□ and R12, particularly preferred are an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylamino group, and an anilio group.

More preferred pyrazoloazole magenta couplers are those in general formulas (If) and (Ig) in which R11 is an alkyl group having 3 to 2 carbon atoms, or an alkoxy group or alkylthio group having 1 to 2 carbon atoms. .

Specific examples of typical magenta couplers and vinyl monomers thereof according to the present invention are shown below, but the invention is not limited thereto.

Shi8 to L17(u) ■-Co■-G H3 -r ■-♂ I-DeI -// I-/- ■-/3 1-/ Da I-/! 1-/ni I-/2 ■ H3 I-no! 1-/ri! −λθ
] Shil ■-22 '-+23 1-. 2<< 1-+2j I N=N 1-+2t [-,27! -+2J' 1-13 UOOCH3■
-+29 1-Jθ H3 [-J+2 ■-33 ■-32 1-ta/ ■-Guko H3 81"117 (tJ -4t3 H3 Represented by the general formula from (Ia) to (re)-j above Examples of coupler compounds, synthesis methods, etc. are described in the documents listed below.

The compound of general formula (Ia) is disclosed in JP-A-Shoj9-/12! The compound of general formula (Ib) in No. -/7/9j
In No. Otsu, the compound of general formula (IC) is disclosed in JP-A No.
No. 62, the compound of general formula (Id) is disclosed in U.S. Patent No. 3,01
7. '132, and compounds of general formula (Ie) are described in US Pat. Nos. 3,72 and 067, respectively.

Also, Tokukai Akira! ♂−&,! θgu! No., Tokukai Akira! 2-/7
7.663, Tokukai Sho! Tar/2g, ♂3 Otsu, Tokukai Akira! Tar/77,! J-issue, Tokukai Sho! ? -/77.66
No. 7, Tokukai Akira! ? -777Jrj≦ issue, JP-A-Shoj9-/
77,! The highly color-forming ballast group described in No. 33 etc. is applicable to any of the compounds of the above general formulas (Ia) to (Ie).

The cyan coupler represented by the general formula CII) used in the present invention will be explained in more detail.

In the general formula [II], R is an aliphatic group having 7 to 3 carbon atoms (e.g., methyl group, butyl group, octyl group, tridecyl group, 1so-hexadecyl group, cyclohexyl group, etc.), an aryl group (e.g., phenyl group, etc.). group, naphthyl group, 2-pyridyl group, corchiazolyl group, cortiazolyl group, caufuryl group, 6-quinolyl group), and these represent an alkyl group, aryl group, heterocyclic group, alkoxy group (e.g., methoxy group, methoxyethoxy group,
Aryloxy groups such as tetradecyloxy-7 groups (e.g., co-, tert-amylphenoxy, cochlorophenoxy, goucyanophenoxy, goubutanesulfo/amidophenoxy groups, etc.), acyl groups (e.g., acetyl groups) , benzoyl group, etc.), ester group (e.g., ethoxycarbonyl group, 2,9-di-tert-amylphenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (e.g., acetyl amino group, butanesulfonamide group, dodecylbenzenesulfonamide M, diflobylsulfamoylamino group, etc.), carbamoyl group (e.g. dimethylcarbamoyl group, ethylcarbamoyl group, etc.), sulfamoyl group (f
l! (e.g., butylsulfamoyl group, etc.), imide groups (e.g., succinimide group, hydantoinyl group, etc.), ureido groups (e.g., phenylureido group, dimethylureido group, etc.), sulfonyl groups (e.g., methanesulfonyl group, carboxymethanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (e.g., butylthio group, phenylthio group, etc.), hydroxyl group,
Cyano group, carboxyl group, nitro group, sulfo group, No1
It may be substituted with a group selected from among the following.

When one or more substituents are present, they may be the same or different.

In the general formula (I[), R4 represents a hydrogen atom, a rogen atom, a lower alkyl group, an aryl group (eg, phenyl group, etc.), or an acylamino group (eg, acetylamino group, etc.).

In the general formula (I [I), R5h aliphatic group (e.g., methyl group, ethyl group, cyclohexyl group, tetradecyl group, etc.), aryl group (e.g., phenyl group, copyridyl group, etc.), heterocyclic group (e.g., /-morpholyl group, etc.), groups), alkoxy groups (e.g., methoxy groups, butoxy groups, etc.), aryloxy groups (e.g., phenoxy groups, etc.),
aliphatic or aromatic thio groups (e.g., butylthio groups,
(a dovylthio group, a phenylthio group, a dodecylthio group, a coimidazolylthio group, etc.) or an acylamino group (for example, a butanamide group, etc.).

R6 and R7 each represent a hydrogen atom or a lower alkyl group.

In the general formula [II], X2 represents a coupling-off group, examples of which include a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), an alkoxy group (e.g., ethoxy group, dodecyloxy group) , methoxyethylcarbamoylmethoxy group, carboxypropyloxy group, methylsulfonyl ethoxy group, etc.), aryloxy group (e.g., cuchlorophenoxy group, q-methoxyphenoxy group, cucarboxyphenoxy group, etc.)
, acyloxy groups (e.g., acetoxy group, tetrazocallyloxy group, benzoyloxy group, etc.), sulfonyloxy groups (e.g., methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide groups (e.g., dichloroacetylamino group, hepta- fluorobutyrylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (sidelight, ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (e.g. phenoxycarbonyloxy ), aliphatic or aromatic thio groups (e.g., ethylthio group, phenylthio group, tetrazolylthio group, etc.), imide groups (e.g., succinimide group, hydantoynyl group, etc.), aromatic azo groups (e.g., phenylazo group, etc.), and so on. These leaving groups may include photographically useful groups.

Furthermore, preferred examples of the cyan coupler represented by the general formula [II] are as follows.

In general formula [Ii), R is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In general formula [II], R5 preferably has a carbon number of /~/
4t alkyl group, arylthio group (e.g., phenylthio group, dodecylphenylthio group, λ-pyridylthio group, etc.) or acylamino group (e.g., acetylamino group, bivalylamine group, etc.), and particularly preferably a group having 7 to 3 carbon atoms. It is an alkyl group. R and R are each preferably a hydrogen atom or a methyl group, and particularly preferably both are hydrogen atoms.

In the general formula ClIn, R4 is preferably a hydrogen atom or a halogen atom, with chlorine and fluorine atoms being particularly preferred.

In general formula [II[], it is particularly preferable that R4 is a chlorine atom, R5 is an alkyl group having /~/q carbon atoms, and R and R7 are both hydrogen atoms.

In the general formula [II], X2 is a halogen atom, an alkoxy group which may have a substituent, an aryloxy group or a sulfonamide group.

In general formula [II], X2 is preferably a halogen atom, particularly preferably a chlorine atom.

Specific examples of the cyan coupler compound represented by the general formula [II] are listed below, but the present invention is not limited thereto.

(n-/) α (ff-, ri(e (II-,,') α (II-1 (II-1) α (■-g) α (II-7) B (n-, l') (II-9) (It-10) di(II-//) (II-/, 2) e (II-/-?) (II-/4t) Red-sensitive emulsion layer preferred for the purpose of the present invention Examples of sensitizing dyes for use are shown below, but the compounds are limited to the exemplified compounds as long as they are sensitizing dyes or combinations of two or more sensitizing dyes that achieve the spectral sensitivity range defined in the claims of the present invention. isn't it.

(4t) (ri(ni) 2H5 ■ (CH2)3S03K (♂) 2H5 (CH2)3SO3Na (CH2)35O3Na (/θ) The method of defining and expressing the relative sensitivity at each wavelength of spectral sensitivity is given by James,・Theory of Photography, Process (T.

H. James, The Theory of t
hePhotographic Process) No. 9
The method described in ed., p. 410 was followed.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mole or less silver iodide. Particularly preferred is about 2 molts to about 2 molts! Silver iodobromide containing up to mol% silver iodide.

Silver halide grains in photographic emulsions include those with regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. It may have crystal defects such as, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.7 microns or less or dog-sized grains with a projected area diameter of up to about 70 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD), A/7, 4t3
(July 2, 2017) 1.22-3 pages, “1. Emulsion preparation
d types)” and the same, A/J'?/
t (/July 979), 4gJ' pages, Graphic "Physics and Chemistry of Photography", published by Beaumontel (P.

Glafkides, Chimie et Physi
quePhotographque Paul Mo
Ntel, /9d7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duf
fin, Photographic Emulsion
Chemistry (Focal Press,
/966), “Production and Coating of Photographic Emulsions” by Zelikman et al.
, Published by Focal Press (V, L, Zelik
Manet al, Making and Coa
tingPhotographic Ernulsio
n, Focal Press.

/ Rigo 4t).

U.S. Patent No. 3. ! 7g, 2! No. 3. Otsu! ! ,
j? Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,4t/3.7gr are also preferred.

Also, Asu's kuto ratio is about! Tabular grains such as those described above can also be used in the present invention. Tabular grains are described by Cutoff, 7 Otographic Science and Engineering (Cutoff).

Photographic 5science and
Engineering).

Volume 1, 24t♂~, 2!2 pages (/70 years); US Patent No. 4tj<t, No. 226, rotation, <t74t
.

No. 370, same group, '133, θri♂ No., Norigu, 4t3
No. 9.620 and British Patent No. 2. It can be easily prepared by the method described in, for example, No. 2,167.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a layered structure. Further, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure A/
7 Otori 3 and Douben/? 2/, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the above two search disclosures, and the locations listed are shown in the table below.

Additive type RD/7 Otsu<t3RD//7/Go/ Chemical sensitizer page 23 Core page 72 right column - Sensitivity increasing agent
Same as above Brightening agent 2♂ Page 7 Anti-staining agent, 2! Page right column Otsu! θ Page left to right column ♂ Dye image stabilizer 2! Page 2 Hardener Page 2 Otsu! /page left column/θ
Binder 2g page Same as above // Plasticizer, lubricant 27 pages 6! θRight column Various color couplers can be used in the present invention, and specific examples thereof can be found in the aforementioned Research Disclosure (RD) publication/2 Gog 3.
, ■-C to G.

As a yellow coupler, for example, U.S. Patent Nos. 3 and 9
No. 33,601, No. 4', No. 022.320, No. g, j, 2! ,, No. 0217, same No. ge, <t.

/, 7! No. λ, Special Publication No. 1987-7073, British Patent No. 1
, Q, 2j, 0.2θ No. 1, 4t7J, 71
Those described in No. 0 etc. are preferred.

As a magenta coupler! -Pyrazolone compounds are preferred, and are disclosed in U.S. Patent No. Q, 310, 4/2,
Same No. 3JR/JR No. 2, European Patent No. 73.4! Particularly preferred are those described in No. B, etc.

Cyan couplers include phenolic and naphthol couplers, which are described in U.S. Pat.

O! λ, No. 272, same No. G, /4tt<, No. 396,
Same No. 1, No. 221.2.33, No. 9.29g, 2θ
θ issue, 2nd and 3rd issue, 9.2nd issue, 2nd issue. ! 0/
, No. 177, Kotsu No. 2 Fuko, No. 732, No. 21/
Riji, 72nd issue, 3.7th! ♂, No. 30♂, No. e
, 3311. , 0// No. q, No. 327.773,
West German Patent Publication No. 3.3.2, No. 722, European Patent No. 1
2/, 34! No. A, U.S. Patent No. 333.922
No., same No. gu, gu! /, No. 66, No. 27, 76
7, European Patent No. 1/2, <A, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available from Research J Disclosure/76 na 3 ■
- Section G, U.S. Patent No. G,/13.

No. 670, Special Publication Show J-7-J9 ¥73, U.S. Patent No. G,
00'l, No. 929, No. G, /31. -231,
Preferred are those described in British Patent No. 1,/4#, Jtr.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 344,2;17, British Patent No. 2, /
2! , No. 370, European Patent No. ! Preference is given to those described in German Patent No. 20, German Patent Publication No. J, 234t, 133.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,4t! /, e! ``2θ, same number, θ♂0.2
// issue, same number '1,367.2! No. ko, British Patent No. ko,
/θ2, /7.1, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is the aforementioned RD/7t
4t 3, patents described in sections ■ to F, JP-A-7-7
! /9 kg, same J-7-7! Gu23q1 60-/♂da, 24t! , U.S. Patent No. 1t, 2g? , Thai No. 2 is preferred.

A coupler that releases a nucleating agent or a development accelerator imagewise during development is disclosed in British Patent No. 2. θri No. 7,790, same No. ko, /3/, /♂! No., Tokukai Akira! Tah/! 2 and 3, same! Preferably, the one described in T./70jrllO.

Other couplers that can be used in the photosensitive material of the present invention include U.S. Pat. Competitive couplers described in U.S. Pat. No. 9,273, U.S. Pat. Multi-equivalent coupler described in t/♂ issue etc., JP-A-Sho gθ-/♂! the law of nature! Examples include DIR redox compound-releasing couplers described in .theta., etc., and couplers that release dyes that recover color after separation described in European Patent Nos. 77J and 302A.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point organic solvents used in the oil-in-ice dispersion method are described in US Pat. No. 2,322.027 and the like.

The process and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. 9゜363, West German Percent License a (OLS) No.;z, rt, t/.

, No. 27q and the same No. 2. ! e/, No. 23θ, etc.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, ya/7 Otsu 4t3's, 2/page and the same, ya/! It is described from the right column of page 64t7 of 77 Otsu to the left column of page 692.

The color photographic material according to the present invention is the above-mentioned RD, Ya/26g 3, Ko♂ to Kota pages and A//7/l, Otsu! / It can be developed by the usual methods described in the left column to right column.

The color photographic material of the present invention is usually subjected to a water washing treatment or a stabilization treatment after development, bleach-fixing or fixing treatment.

In the washing process, two or more tanks are generally used for countercurrent washing to save water. As a stabilizing treatment, Tokukai Sho is used to wash the water in the washing process! 7-♂! A typical example is a multistage countercurrent stabilization treatment as described in No. 4t3.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color base 76-, color positive film, and color reversal paper. The present invention is particularly preferably used for color reversal photosensitive materials.

(Examples) The present invention will be further described below based on Examples, but the present invention is not limited thereto.

Example 1 On a subbed cellulose triacetate film support,
A multilayer color photosensitive material consisting of each layer having the following composition was prepared and designated as sample /θ/.

1st layer: antihalation layer black colloidal silver θ, 2jg/m2 UV absorber U-10, 0g/m2 UV absorber U-co θ, /g/m2 UV absorber U-30, /g/ rnZ High boiling point organic solvent 0- / 0, / cc/
Gelatin layer containing m2 (dry film thickness μ) 2nd layer; intermediate layer compound H-/o, o, tg/m2 Gelatin layer containing high boiling point organic solvent 0-2 0, 03 cc/m2 (dry film thickness /μ) 3rd layer; 1st red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-/ and S-s Silver amount...θ, tg/m2 (iodine content gmolt, average particle size 0.3μ) coupler C-/θ, λg/m2 coupler C-,2o, otg/m2 high-boiling organic solvent 0-. 2
Gelatin layer containing θ, /x cc/m2 (dry film thickness/μ) Qth layer: Red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-/ and S-s Silver Amount...0. Coupler C-/o, rtg/m2 Coupler C-xo, 7927m2 High-boiling organic solvent 0-20, j3 cc/m
Gelatin layer containing 2 (dry film thickness, jμ): Interlayer compound H-/0.7 g/m2 Gelatin layer containing high boiling point organic solvent 0-20,/cc/rn2 (dry film thickness/ μ) 6th layer: First green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-<t Silver amount...θ, 7 g/m2 (iodine content 3 molt, Average particle size 0.3μ) Coupler C-30, jjg/m2 High boiling point organic solvent 0-2 0. ．． Gelatin layer containing 24 cc/m2 (dry film thickness/μ) 2nd layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dye S-3 and S-<t Silver amount...・0.7 g/m2 (iodine content λ,
! Molch, average particle size o, a”μ) coupler C-ta 0.2 g/m2 Gelatin layer containing high boiling point organic solvent 0-, 2o, θjcc/m2 (
Dry film thickness 29! μ) rth layer: intermediate layer compound H-/θ, 0! g/m2 Gelatin layer containing high boiling point organic solvent 0-,z O,/g/m2 (dry film thickness/μ) 9th layer: Yellow filter layer Yellow colloidal silver 0. /g/m2 compound
H-10,0g/m2 Compound H-20,03g/m2 High-boiling organic solvent 0-. Gelatin layer containing 2o, θgcc/m2 (dry film thickness/μ) 70th layer: 7th blue-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dye S-t Silver amount...
・0.6g/m2 (Contains iodine,!Molti, average particle size 0.7μ) Coupler C-10,! g/m2 High boiling point organic solvent 0-20, / cc/m2
Gelatin layer containing (dry film thickness/, !μ) 1st/layer: Blue-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dye S-t Silver amount...
・/, /g/m2 (Iodine-containing -f,2,jmolti, average particle size 7.2μ) Gelatin containing coupler C-j/, Jg/m2 High boiling point organic solvent 0-20, 23 cc/m2 Layer (dry film thickness 3μ) 1st co-layer: 1st protective layer UV absorber U-10. o g/m2 Ultraviolet absorber U-20,03 g/m2 Ultraviolet absorber U-30,03 g/m2 Ultraviolet absorber U-4t o, sqg/m2 High boiling point organic solvent 0-/ θ, Co J'cc/ Gelatin layer containing m2 (dry film thickness μ) 73rd layer: Fine grain silver iodobromide emulsion covered with the second protective layer surface Silver amount...0. /g/m2 (Iodine content: 1 molty, average particle size: 0.06μ) Gelatin layer (dry film thickness θ, !μ) containing polymethyl methacrylate particles (average particle size: /,!μ) Each layer contains the above composition. Additionally, gelatin hardener H-3 and surfactant were added.

The compounds used to prepare the samples are shown below.

C-/ -J C-g CH3 -t U-/ U-,2 U-g H-/ CH2=CH8O2CH2CONHCH2CH2=CH
3O2CH2CONI-■CH2S-co5-j S-goo-z The color development process used in this example is as follows.

Processing process Process Time Temperature First development 6 minutes 3!0C Water washing time Reversal 2 minutes Color development 6 minutes Adjustment amount Bleach white 3 minutes Fixed arrival time: 9 minutes Water washing time Stable for 7 minutes at room temperature drying The composition of the treatment liquid used is as follows.

No.-Developer water 700
m1 Nitrilo-N,N,N-trimethylenephosphonic acid pentatrilam salt Cog Sodium sulfite, 20g Hydroquinone monosulfonate 30g Sodium carbonate (-hydrate) 30g/-Phenylugmethyl-9-hydroxymethyl-3 Pyrazolidone - 2g potassium bromide! g Potassium thiocyanate /, 2 g Potassium iodide (0.7% solution) Add 2 ml water
/θ00m1 Inverted liquid water 700
m1 Nitrilo-N,N,N-trimethylenephosphonic acid penta-sodium salt 3g stannous chloride (trihydrate) /gp-aminophenol 0.1g sodium hydroxide
2g glacial acetic acid
Add 73ml water to make 7000ml
Color developer water 700m
1 Nitrilo-N,N,N-trimethylenephosphonic acid pentatrilam salt 3g Sodium sulfite 2g Sodium triphosphate (/, dihydrate) 33g Potassium bromide 7g Potassium iodide (
0.7% solution) Sodium hydroxide
3g citradinic acid
/,! gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-9-aminoaniline sulfate //g3.6-cythiaoctane-/.

! -Diol 7g Add water to 1000ml Adjustment liquid water 700ml
1 Sodium sulfite 7.2 g Ethylenediaminetetraxanatrirum (technical water salt) rg Thioglycerin 0, ml Glacial acetic acid
Add 3 ml water
10θOm1! bleach solution water 10
0g ethylenediaminetetraacetic acid xaliram (technical water salt) 2g ethylenediaminetetraacetic acid iron (I [[)] Ammonium (technical water salt) 720g potassium bromide 700g Add water
/θθOml fixer water J'00
m1 Sodium thiosulfate 20.0g Sodium sulfite r, og Sodium bisulfite! , θg water added
10100O stable liquid water ♂θOm
l Formalin (37 weight c4) j, θml Fuji Drywell (surfactant manufactured by Fuji Film ■) j, Oml Add water to 1000ml1 then sample 10
Samples 10 to /Q♂ were prepared by changing the couplers in the third and ninth layers, the couplers in the sixth and seventh layers, and the sensitizing dyes in the third and ninth layers.

The composition of these samples is shown in Table/.

The following tests were carried out for samples 10/~/Dr obtained in Table 7.

(Test/) Evaluation of color reproducibility Photograph a subject containing red and purple colors, perform the color development process described above, and measure the cyan density of each part using a Macbeth densitometer. Especially the desire. The higher the cyan density is, the better the reproducibility of purple is, and the lower the cyan density is, the better the saturation of red is.

(Test 2) Evaluation of Color Image Preservability The sample obtained in Test 1 was stored in a thermostatic chamber at 100°C, taken out after 78 days, and the cyan concentration in the purple part was measured again using a Macbeth densitometer.

The results of (Test/) to (Test, 2) are shown in Table 2.

As is clear from Table 2, Combination K of the present invention improves the reproducibility of purple and red colors, which was difficult in the past, including over time.

In other words, as shown in Comparative Example Test 14ioi, in the past, it was difficult for cyan to enter the purple part, resulting in a reddish, dark purple color, and cyan tended to enter the 10,000-yen ticket, resulting in a muddy red color. In the comparative example sample 10t, both purple and red data before aging (Cpl) were improved, but after aging at 10O0C for 7 days, the superiority could not be maintained, and rather the cyan concentration in purple (Cpz) was lower than that of this example. It falls into the lowest category among the samples. On the other hand, the sample lor related to the present invention belongs to the group with the highest cyan concentration in both the data before aging (Cpl) and the data after aging (Cpz), and the cyan concentration in the red part is low, which is the object of the present invention. has been achieved.

EXAMPLE A paper support laminated on both sides with copolyethylene was coated with the following 1! A color photographic light-sensitive material was prepared by applying the first layer starting from 'm' in multiple layers. The coating side of the first layer of polyethylene contains titanium white as a white pigment and a small amount of ultramarine blue as an evening dye.

(Photosensitive layer composition) The components and coating amount in units of 2/m2 are shown below. Regarding silver halide, the coating amount is shown in terms of silver.

i-th layer (antihalation layer) Black colloidal silver...1 mark, o, i.

Gelatin ・・・・・・・・・2.
0 Second layer (low-sensitivity red-sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dye (*Yoto*Hiro) (silver iodide 3.!molar, average grain size 0.7μ)
・・・・・・・・・Silver 0. /! gelatin
・・・・・・・・・／, 0 cyan coupler (
*3) ・・・・・・・・・083゜Anti-fading agent (*ko) ・・・・・・・・・θ, /! Coupler solvent (*l*l)・・・・・・o, ot 3rd layer (highly sensitive red sensitive layer) Iodine spectrally sensitized with red sensitizing dye (*yoto*≠) Silver iodide emulsion (silver iodide r, o mole, average grain size 0.7μ)
・・・・・・・・・Silver 0. IO gelatin
・・・・・・・・・0. jO cyan coupler (*3) ......0.10 Anti-fade agent (*2) ......0.02 Coupler solvent (*/r and *l)...・・・・・・0.02
μth layer (intermediate layer) Yellow colloidal silver ・・・・・・・・・0.
θ cogelatin ・・・・・・・・・
i, o.

Color mixing prevention agent (*/≠) ・・・・・・・・・0.
Or color mixing inhibitor solvent (*/J) ・・・・・・・・・
・o, it polymer latex (*l) ・・・・
...o, i.

5th layer (low sensitivity green sensitive layer) Spectrally sensitized with a green sensitizing dye (*/co) and then silver iodobromide emulsion (silver iodide, ! morch, average grain size O1μμ)
・・・・・・・・・Silver 0. ．． 20 gelatin
・・・・・・・・・0.70 Magenta coupler (*//) ・・・・・・・・・0. μ0 anti-fading agent A (*10) ・・・・・・・・・o, o
r Anti-fading agent B (*ri) ・・・・・・・・・0
．． 0/Anti-fading agent C (*a')...
...0.02 turnip 2-solvent (*7) ...
...Q,/! Layer (high-sensitivity green-sensitive layer) Silver iodobromide emulsion spectrally sensitized with a green sensitizing dye (*/, 2) (silver iodide 3.! molten, average grain size O0 μ)
・・・・・・・・・Silver 0.20 gelatin
・・・・・・・・・0.70 Magenta Kazolar (*/l) ・・・・・・・・・o, Guθ anti-fading agent A (*10) ・・・・・・・・・0.0
2 Anti-fading agent B (*ri) ・・・・・・・・・0
．． 0/Anti-fading agent c (*J') ・・・・・・
...0.02 coupler solvent (*7) ...
・Dan・0. /j 7th layer (yellow filter layer) Yellow colloidal silver - - - - - 0, J O gelatin /, 0θ
Color mixing prevention agent (*/a)...Group・0.0
6 Color mixing prevention agent solvent (*/J) ・・・・・・・・・
0.2≠Irradiation prevention dye (*, 2J, 4c2
≠) Layer (low-sensitivity blue-sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (*/A) (silver iodide λ, !molch, average grain size O0jμ)
・・・・・・・・・Silver o, ij gelatin
・・・・・・・・・0. j0 yellow chi
Coupler solvent (*/I) ・・・・・・・・・0.02
5th P layer (high sensitivity green sensitive layer) Spectrally sensitized with blue sensitizing dye (*/&), silver iodobromide emulsion (silver iodide 2.j mol, average grain size/, 4Lμ)
・・・・・・・・・Gin O, Ko O Zewochi/
・・・・・・・・・・・・θ, jθ Yellow color (*/yo) ・・・・・・・・・0.20 Coupler solvent (*l!r) ・・・・・・...0.
0! No. io) Threat (ultraviolet absorption layer) Gelatin ・・・・・・・・・i,
r.

Ultraviolet absorber (*/ri) ・・・・・・・・・i,
.

Ultraviolet absorber solvent (*/r) ・・・・・・・・・0
．． JO color mixing prevention agent (*/7) ・・・・・・・・・
・・0.0 as 1st/layer (protective layer) Fine grain silver chlorobromide (silver chloride 77 molti, average particle size 0
．． 2μ) ・・・・・・・・・0.07 Gelatin ・・・・・・・・・／、0 Hardener (*20) ・Old・・・・・・0. /7 The compound used here is 2*/dioctyl phthalate*, 2-co(2-hydroxy-j-3ec-butyl-z-t-butylphenyl)benzotriazole*3 2-(α -(2,Hiro-di-t-amylphenoxy)butanamide]-≠,t-dichloro-!-methylphenol*4 t,j'-dichloro-3,3'-di(3-sulfobutyl)-terethylthia carbonyl cyanine sodium
salt*! Triethylammonium-J-r:x-(Co[3
-(3-sulfopropyl)nando(/,2-d)thiazoline-coylidenemethyl]-7-butenyl)-3-naphtho(t,2-d)thiazolino]propanesulfonate*B Polyethyl acrylate*7 Phosphoric acid Trioctyl ester *r 2. ≠-di-t-hexylno)hydroquinone*t-(,2-hydroxy-J-t-butyl-yo-methylphenyl)methane*10! ,3.3',j,-tetramethyl-!
.

t, r', t'-tetrapropoxy-/.

l'-bisspiroindane*// /-(2,≠, monotrichlorophenyl)-
3-(Coke α-low-tetradecanamide) Anilino-Virazolino! -On*/ko! , J″-diphenyl-terethyl-3゜3′
-Disulfoprobyloxacarbonanion Na salt*/3 Phosphoric acid-0-cresyl ester*/≠ 2. Hiro-ji t-octylno-hydroquinone*lj α-piparoyl-α-[(2,≠-dioxo/-benzyru-yo-ethoxyhydantoin-3-yl)-Coke α-low! -(α-λ,≠-dioxo-t-amylphenoxy)butamino]acetanilide*/J)'Jethylammonium 3-[λ-(3-benzylrhodanine-ylidene)-3-benzoxazolinyl] Furono ξ sulfonate */7 u,≠-di-5ec-octylhydroquinone */II)
Butyl-1-1-octyl)phenylbenztriazole *λθ /, 4t-bis(vinylsulfonylacetamido)ethane *2/ λ-[α-(-, googe-t-amylphenoxy)butanamide-≠, 6-dichloro- 1 ethylphenol*, 2.2+-chloro-2-(2-chlorobenzamide)-j-Cα-(≠-t-amyl-2-chlorophenoxy)octanamide]phenol*23 *2 hirobsu 3 艮 S The sample prepared as described above in Step 3 was designated as sample number 20/, and this was used as a reference sample for subsequent comparisons.

Couplers in the second and third layers of sample number λoi, ! .

By replacing the coupler in the layer and the sensitizing dye in the second and third layers, samples 2 to 1LL were prepared.

The composition of samples 20/~ko/hiro is shown in Table 3.

Compounds used for sample separation and λ/2 (Unexamined Japanese Patent Publication No. 6/-/A
7ri J-u, JP-A-60-23-2-2 J-0) **l **λ 3.3'-di(r-sulfopropyl)-7-methyl-thiadicarpocyanine sodium The color development process used in this example is as follows.

[Processing process]

First development (black and white development) Jr'CI'/Yo'water
Wash J roc/' 3011
Reverse exposure 100 Lux or more Color development 3♂oC2'/j'' Water washing
3r0c Hiroyo “bleach fixed i J, r’C2’ 00” water wash
3r0c x'ij" [Processing solution composition] 1st developer nitriloN, N, N-)rimethylenephosphonic acid, pentasodium salt 0.z1 Diethylenetriaminepentaacetic acid, pentasodium salt ≠, O? Potassium sulfite 30.Of Potassium thiocyanate 1. λ is potassium carbonate
3jt, 0? Hydroquino/monosulfonate potassium salt 2j, Of? Diethylene glycol I! , 0gol-phenyl-≠
-Hydroxymethyl-Hiro-Methyl-3-pyrazolidone Ko, 0? Potassium bromide 0. ,! r? Kajipotassium iodide! , O Add water
1t (pH 2,70) Color developer benzyl alcohol /j, 0rnl diethylene glycol /co, Ogoj, 4-dithia/,? -Oftanediol θ, co2nitriloN, N, N-trinotylenephosphonic acid pentatrilam salt θ,jP diethylenetriaminepentaacetic acid pentasodium salt 2.02 Sodium sulfite 2.02 Potassium carbonate
2! , 0? Hydroxylamine sulfate 3,02N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-Hiroshi-aminoaniline sulfate! , 07 potassium bromide 0.51 potassium iodide
/, 0 ■ Add water
/ t (pH 10, jO) bleach-fix solution 11 merkabutol, 3. Gatetriazole /, 02 Ethylenediaminetetraacetic acid disodium dihydrate jt, 0? Ethylenediaminetetraacetic acid/Fe(III)/77monium hydrate to, o
r Sodium sulfite /! , 0? Sodium thiosulfate (yooyll solution) / Ao, o glacial acetic acid
z, add oml water
/t(pHA,jO) The nine samples obtained were subjected to (Test 3) and (Test 2) as shown in Example/.

(Test 3) As a transparent original, a color slide with red and purple color markers obtained from Fujichrome Pro 7 Edge Reversal Film (RDP) (manufactured by Fuji Photo Film) was used to create prints from the transparent original. hole. The cyan reflection density of the red and purple parts of the nine prints obtained was measured, and the color reproducibility was evaluated in the same manner as in (Test 2).

The results of (Test 3) and (Test 2) are shown in the table below.

As is clear from Table μ and Table 4, the object of the present invention was not achieved in any of the comparative examples of sample 20/-2//. 679j2
And JP-A-2012-23,2! However, in all cases, the cyan concentration in the purple color is low, and the reproducibility of the purple color is poor. Sample 20 again! r-207 has a high cyan concentration in purple and a low cyan concentration in red,
Although the results are good in terms of color reproduction, the 777m degree in the purple color has decreased significantly over time compared to the others. On the other hand, it can be seen that Samples Co/2 to Co/2/G of the present invention all had improved color reproducibility and color image storage stability, and that the objects of the present invention were achieved.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment 1/73/2019 Case Indication 1936/2009 Patent Application No. 2 to 79r
No. 2, Title of the invention Silver halogenide color photographic light-sensitive material 3. Relationship with the person making the amendment Patent applicant Address 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment Akira
The description in the "Detailed Description of the Invention" column 5 of the +1E document and the "Detailed Description of the Invention" section of the Statement of Contents of the Amendment is amended as follows.

1) Page t7 λ ~ line 3 After “Hydroquinone Monosulfonate” "= Potassium salt" Insert.

2) On page 70, line B to line 7, [Fuji Drywell (surfactant made by Fuji±Film■) to correct.

3) Insert the attached sheet -/ after the 17th line of page 7≠.

4) Insert the description in Attachment -λ after the 13th line of the octopus page.

Attachment 7 [Similar tests were conducted on samples ioi to ior, with the following treatments only, and similar results were obtained.

Processing process Time Temperature first development 6 minutes 3. r0C first water wash
l/L! Seconds 31 1 inversion ≠lx
3g 1 color development minute 3t l bleach 2z 31 # white fixing 4tz 31 1 second washing fil
/I 3II 2nd water wash (21/# 3(
z Stable /I 2j1 The composition of each treatment liquid was as follows.

No. 1 - Current iron solution Nitrilo N, N, N-tri-101 Methylenephosphonic acid/j sodium salt Sodium sulfite 30? Hydroquinone/potassium monosulfonate 20? Potassium carbonate 332/-phenyl-≠
-Methyl- -902G hydroxymethyl-3 -Pyrazolidone beautifying potassium K, j1 Potassium thiocyanate - /, -2 Potassium iodide
Add λ, om9 water
/ 000gopH2,t.

pH was adjusted with hydrochloric acid or potassium hydroxide.

First washing liquid mother liquor Ethylenediaminetetramethane 2.0? Renphosphonate Conosodium Phosphate! ,01Add water to 1000mlpH7.0
0 pH was adjusted with hydrochloric acid or sodium hydroxide.

Hg not adjusted.

Reversal liquid methylenephosphonic acid, j sodium salt, stannous chloride, cohydrate salt /,0ffp-aminephenol (7,/S'sodium hydroxide ??glacial acetic acid
/j Add water
1000 go pHt, o.

pH was adjusted with hydrochloric acid or sodium hydroxide.

Color developer Nitrilo-NIN, N-tri λ, Of methylene phospho/acid! Sodium salt Sodium sulfite 7.0? phosphoric acid 3
Sodium/decahydrate 36f! potassium bromide
/, Of potassium iodide
20 ■ Sodium hydroxide
3.0? Citrazic acid
/,! 2N-ethyl-N-(β-meta //
ft-sulfonamidoethyl) -3-methyl-≠-amine aniline sulfate 3.6-cythiaoctane/, /, 0ft-
Diol H//, rO pH was adjusted with hydrochloric acid or potassium hydroxide.

Bleach solution ethylenediamine≠acetic acid・2 10.0#sodium salt・cohydrate salt ethylenediamine hydroacetic acid・/, 2 (7SFF
e(n[)・Ammonium hydroxide Ammonium bromide 1009 Ammonium nitrate 10? bleach accelerator
o, ooz mole water plus
1ooogo pHA, 3゜pn was adjusted to fA with hydrochloric acid or aqueous ammonia.

Bleach-fix solution Fe(), ammonium, cohydrate, ethylenediamine fluoroacetic acid, λ! ,02 Sodium λ hydrate Sodium thiosulfate rotSodium sulfite /ko,oy Add water
10100O+)H1,,60 pn was adjusted with hydrochloric acid or aqueous ammonia.

The second washing liquid tap water was mixed with an H-type strongly acidic cation exchange resin (Amberlite IR-/2OB manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-≠00).
) was passed through a hotbed column packed with calcium and magnesium ions to a concentration of 3 m9/l, followed by isocyanuric dichloride (orrv)/l.
and sodium sulfate/,! flt was added. p of this liquid
u is 6. ! ~7. It is in the range of j.

Stabilizing liquid formalin 37% r, o polyoxyethylene-p-mono Ooyoml nonylphenyl ether (average degree of polymerization IO) Add water 1000rrtlp
1 (11 not adjusted) Attachment 1 "Same results were obtained when the same test was conducted on Samples 07 to 214L with only the treatment changed as shown below.

Phenomenon 1 60 seconds 3r0C first water washing
tol 33 1 color development TaQz
Jl 0Cm white 601 31 #Bleach constant i 601 311 Second washing 401 331 The composition of each treatment solution is as follows.

1. Developer solution mother solution Replenisher solution Nitri o-N, N, N 1. oy /, o
y-trimethylenephosphonic acid! Sodium salt diethylenetriamine j, Of j, Of
! Acetic acid! Sodium salt potassium sulfite! 0. Of Jo, 0?
Potassium thiocyanate /, 2t /, JP potassium carbonate, 3j, Of! j, Of
Hydroquinone monos λj, Of 2! , 0?
Potassium sulfonate/-phenyl-3 ~ pico, oy, x, oy lazolidone potassium bromide o, ry - potassium iodide yo-omy - add water 10100O1000mlpH ta, to
The pH was adjusted to 70 with hydrochloric acid or potassium hydroxide.

First washing liquid Mother liquor Replenishment solution acid Lambda sodium phosphate s, oy Add water 1000M pH7, o.

The pH was adjusted to v4 with hydrochloric acid or hydroxide.

Color development mother solution Replenisher diethylene glycol /, 2.0ml /≠,
ogo j, J-ji f7-/, 2.0Of? 2
．． 60? r-octanenitri O-N,N,N O,j? 0.6
? -trimethylenephosphonic acid J sodium salt diethylenetriamine 2. Of, 2. Of
j Acetic acid/sodium salt Sodium sulfite 2.0? 2. j?
Hydroxylamine sulfur 3.0? j, AP
Acid acid N-x chill-N-(βt,o) 9.09
-methanesulfonamidoethyl)-3-methyl-aminoaniline sulfate ethylenediamine 10. Ome/ko, O
Go fluorescent whitening agent (Diami /, Of /, λ
? Nostilbene type) Potassium bromide o, ry - Potassium iodide / , Om, 9 - Add water to 1000ml pH 10, tO /
/,00 pHId,,adjusted with hydrochloric acid or woodblock potassium.

bleaching solution Mother liquor Replenishment solution Acetic acid/conatorium mu salt Ethylenediamine≠ /λ02 Acetic acid/Fe ([1) ・Ammonium・ water salt Ammonium bromide 100? Ammonium nitrate 10? Add water 1000vrlpH6,30 The pH was adjusted with acetic acid or aqueous ammonia.

Bleach-fix solution Mother solution Replenisher Ethylenediamine ≠ Vinegar! , 02 The same acid in the mother liquor.
Co-sodium/co-hydrate ethylene diamine hydroxide to, oy acid/Fe(I)
[I) Ammonium/Hydrate Sodium Sulfite No, 0? Ammonium thiosulfate /Ail) ml (yoo?
/l) λ-mercapto/, O8! ? 31 Hiro - Add triacy water to 7000ml pH & 1
0 Be sure to adjust the pH with acetic acid or aqueous ammonia.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer on a support, wherein at least the green-sensitive emulsion layer has the following: The red-sensitive emulsion layer contains at least one coupler represented by the general formula [I], and at least one coupler represented by the following general formula [II] is contained in the red-sensitive emulsion layer. The wavelength showing the highest spectral sensitivity is in the range of 600nm to 650nm, and the wavelength corresponding to 30% of the highest spectral sensitivity is 550nm.
A silver halide color photographic material characterized in that the wavelength is in the range of m to 680 nm. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Za and Zb are ▲There are mathematical formulas, chemical formulas, tables, etc.) or =N-, and R_1 and R_2 are hydrogen atoms or substitution group, and X_1 represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. When Za=Zb is a carbon-carbon double bond, it is an aromatic ring. It may be a part of R_1R_2 or 3 represents an aliphatic group, an aryl group, or a heterocyclic group which may have a substituent, and R^4 represents a hydrogen atom, a halogen atom, an alkyl group, or an acylamino group. R^5 is an aliphatic group. , represents an aryl group, a heterocyclic group, an aliphatic oxy group, an aliphatic thio group, an aryloxy group, an arylthio group, or an acylamino group, and R^6 and R^7 may be the same or different from each other, and a hydrogen atom or (Represents a lower alkyl group. X_2 represents a group that can be separated during the coupling reaction with the oxidized form of the developing agent.)